Valerolactone compounds and perfume composition

ABSTRACT

A valerolactone compound represented by the formula (I):  
                 
 
wherein each of R 1  and R 2  is independently a hydrogen atom, a methyl group or an ethyl group wherein when R 1  is a hydrogen atom, R 2  is not a hydrogen atom; and wherein when R 2  is a hydrogen atom, R 1  is not a hydrogen atom, R 3  is a hydrogen atom or a methyl group, and R 4  is a propyl group, a 1-propenyl group or a phenyl group; a valerolactone compound represented by the formula (II):  
                 
a process for preparing the same; and a perfume composition comprising the above-mentioned valerolactone compound.

TECHNICAL FIELD

The present invention relates to a valerolactone compound and a processfor preparing the same, and a perfume composition containing thevalerolactone compound.

BACKGROUND ART

Sandalwood (Japanese name: Byakudan) which has been mainly produced inthe eastern district of India has a noble characteristic odor.Therefore, sandalwood has been highly prized as a material for Buddhiststatues and various craft carving materials in the Orient. An essentialoil obtained from the core and root of the sandalwood by water steamdistillation has been used as a perfume from old times. Thecharacteristics of this sandalwood oil reside in that the sandalwood oilshows a soft and sweet woody odor and a balsamic odor, and has highsustainability odor. Therefore, the sandalwood oil has been widely usedin oriental-type fragrance, perfume, cosmetics, soap, incense stick andthe like (for example, see “Fundamental Knowledge of Perfumes and FlavorPreparation” authored and edited by Mototaka Nakajima, Sangyo-tosyoKabushiki Kaisya, initial edition third printing (2000), p. 322-323).

However, with increased consciousness on environmental protection, andreinforcement of forest protection as flood control measures in recentyears, there is a tendency that excessive felling of natural timber issuppressed. The amount of felling of sandalwood is restricted by thegovernments in the countries producing it, and deficient supply and costincrease of sandalwood oil has become a problem in the fragranceindustry.

For this reason, as a substitute for sandalwood oil, sandalwood-typearoma chemicals such as2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol,2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol,3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-pentan-2-ol, andisocamphylcyclohexanol have been used. However, these sandalwood-typearoma chemicals are deficient in the soft and characteristic sweet odorof natural sandalwood. Therefore, it is difficult to sufficientlyreproduce the odor of natural sandalwood.

Generally, as a perfume supplementary to the sweet flavor of a perfumecomposition, there have been proposed esters, lactones, faranons,vanillins, and the like. Among them, lactones, for example,γ-pentyl-γ-butyrolactone (another name γ-nonalactone) andδ-pentyl-δ-valerolactone (another name δ-decalactone) have coconut-likeand milk-like sweetness. Therefore, the lactones exhibit effects ofproducing food-like sweetness. It is said thatγ-ethyl-γ-1-butenyl-δ-valerolactone (for example, seeJP-A-Showa-53-84975) is costus-like lactone, and that saturatedγ-ethyl-γ-butyl-δ-valerolactone (for example, trade name: COSTAULONmanufactured by PFW) is costus-like and woody-like lactone.

In addition, as a lactone compound which can be used as a perfume,4-cyclohexylpentanolide (for example, see JP-B-Showa-62-5123) andα-alkyl-β-alkyl-δ-alkyl-δ-valerolactone have been known (for example,see U.S. Pat. No. 3,380,457).

As explained above, since many of the above-mentioned lactones have nowoody odor, even when the lactones are directly added to sandalwood-typearoma chemicals, the harmony of perfumes are insufficient, and moreover,food-like sweetness impairs the characteristics of the naturalsandalwood. In addition, among the lactones, those having a woody odorshow a strong costus-like odor, and are insufficient in sweetness.Therefore, even when they are added to sandalwood-type aroma chemicals,sweetness having a natural sandalwood-like sweetness cannot besupplemented. In other words, conventionally, the perfume compositionshaving a characteristic soft and sweet woody and balsamic odor ofnatural sandalwood have not yet been artificially obtained.

DISCLOSURE OF INVENTION

The present invention relates to a valerolactone compound represented bythe formula (I):

wherein each of R¹ and R² is independently a hydrogen atom, a methylgroup or an ethyl group wherein when R¹ is a hydrogen atom, R² is not ahydrogen atom; and wherein when R² is a hydrogen atom, R¹ is not ahydrogen atom, R³ is a hydrogen atom or a methyl group, and R⁴ is apropyl group, a 1-propenyl group or a phenyl group.

SPECIFIC EXPLANATION OF INVENTION

More specifically, the present invention relates to a valerolactonecompound which emits a lactone-like odor having coumarin-like sweetnessreminding a woody and tonka beans-like odor, and is excellent inlong-lasting effect, and a perfume composition containing theabove-mentioned valerolactone compound, which exhibits characteristicsof natural sandalwood.

The present inventors have found that a valerolactone compoundrepresented by the formula (I) described below emits a characteristicodor having both a woody and a coumarin-like sweet odor, that the odorcan bring out a sweet odor harmonized with a woody odor, and thatcharacteristics of natural sandalwood which have been insufficient insandalwood-type aroma chemicals can be easily exhibited when thevalerolactone compound is particularly combined with a sandalwood-typearoma chemicals.

Also, a valerolactone compound represented by the formula (II) of thepreset invention can be prepared by acting a base on propanal, andtreating the resulting reaction solution with an acid. Alternatively,the valerolactone compound represented by the formula (II) of thepresent invention can be prepared by acting a base on2-methyl-2-pentenal, and treating the resulting solution with an acid.

The present invention enables to provide a perfume composition having asweet odor harmonized with a woody odor by including the valerolactonecompound represented by the formula (I) in the composition. Moreover,the present invention enables to impart a sweet odor matching with awoody odor close to that of natural sandalwood to household products,personal care and cosmetic products, environmental hygiene products,beverages and foods by including the perfume composition in thoseproducts.

The valerolactone compound of the present invention is

-   (1) a valerolactone compound represented by the formula (I):    wherein each of R¹ and R² is independently a hydrogen atom, a methyl    group or an ethyl group wherein when R¹ is a hydrogen atom, R² is    not a hydrogen atom; and wherein when R² is a hydrogen atom, R¹ is    not a hydrogen atom, R³ is a hydrogen atom or a methyl group, and R⁴    is a propyl group, a 1-propenyl group or a phenyl group.-   (2) Also, the valerolactone compound of the present invention is a    valerolactone compound represented by the formula (II):-   (3) The valerolactone compound of the present invention is a    valerolactone compound represented by the formula (II) obtained by    acting a base on propanal, and treating the resulting reaction    solution with an acid.-   (4) The process for preparing the valerolactone compound of the    present invention is a process for preparing a valerolactone    compound represented by the formula (II), which contains acting a    base on propanal, and treating the resulting reaction solution with    an acid.-   (5) The process for preparing the valerolactone compound of the    present invention is a process for preparing a valerolactone    compound represented by the formula (II), which contains acting a    base on 2-methyl-2-pentenal, and treating the resulting reaction    solution with an acid.-   (6) The perfume composition of the present invention is a perfume    composition which contains a valerolactone compound represented by    the formula (I).-   (7) The perfume composition of the present invention is a perfume    composition which contains a valerolactone compound represented by    the formula (II).-   (8) The perfume composition of the present invention is a perfume    composition which contains a valerolactone compound described in the    above item (3).-   (9) The perfume composition of the present invention is also a    perfume 20 composition which contains one or more compounds selected    from the group consisting of the compounds represented by the    following formulae (III) to (VII):-   (10) Further, the perfume composition of the present invention is a    perfume composition which contains two or more compounds selected    from the group consisting of the compounds represented by the    following formulae (III) to (VII).-   (11) Further, the perfume composition of the present invention is a    perfume composition which contains a perfume of which main starting    material is camphorenal.-   (12) Further, the perfume composition of the present invention is a    perfume composition according to any one of the above item (6) to    (8), which contains one or more compounds selected from the group    consisting of Component (A):    2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol,    3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol,    3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-pentan-2-ol,    2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-butanol,    3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol,    3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol,    2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol and    optical isomers thereof.

The present invention relates to:

-   (13) a household product containing the perfume composition    according to any one of the above items (6) to (12),-   (14) a personal care and cosmetic product containing the perfume    composition according to any one of the above items (6) to (12),-   (15) an environmental hygiene product containing the perfume    composition according to any one of the above items (6) to (12),-   (16) a beverage containing the perfume composition according to any    one of the above items (6) to (12), and-   (17) a food containing the perfume composition according to any one    of the above items (6) to (12).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an ¹H-NMR (400 MHz) chart ofα-methyl-γ-methyl-γ-1-propenyl-valerolactone.

FIG. 2 is a graph showing the results of measurement of an infraredabsorption spectrum of α-methyl-γ-methyl-γ-1-propenylvalerolactone.

FIG. 3 is an ¹H-NMR (400 Mz) chart ofβ-ethyl-γ-methyl-γ-1-propenyl-valerolactone.

FIG. 4 is a graph showing the results of measurement of an infraredabsorption spectrum of γ-ethyl-γ-methyl-γ-1-propenylvalerolactone.

FIG. 5 is an ¹H-NMR (400 MHz) chart ofα-methyl-β-ethyl-γ-methyl-γ-phenyl-valerolactone.

FIG. 6 is a graph showing the results of measurement of an infraredabsorption spectrum of α-methyl-β-ethyl-γ-methyl-γ-phenylvalerolactone.

FIG. 7 is a graph showing the results of measurement of an infraredabsorption spectrum ofα-methyl-β-ethyl-γ-methyl-γ-1-propenyl-δ-valerolactone obtained inExample 4 of the present invention.

FIG. 8 is a graph showing the results of measurement of ¹H-NMR (CDCl₃)of α-methyl-β-ethyl-γ-methyl-γ-1-propenyl-δ-valerolactone obtained inExample 4 of the present invention.

FIG. 9 is an ¹H-NMR (400 MHz) chart ofα-methyl-β-ethyl-γ-methyl-γ-propyl-δ-valerolactone.

FIG. 10 is a graph showing the results of measurement of an infraredabsorption spectrum ofα-methyl-β-ethyl-γ-methyl-γ-propyl-δ-valerolactone.

BEST MODE FOR CARRYING OUT THE INVENTION

The valerolactone compound of the present invention is represented bythe formula (I), and has a sweet odor useful as a perfume substance.

Among the compounds resented by the formula (I),α-methyl-γ-ethyl-γ-methyl-γ-1-propenyl-δ-valerolactone resented by theformula (II) is especially preferable since this compound itself hasboth a woodsy odor and a coumarin-like sweet odor which reminds of tonkabeans, and is easily harmonized with a woodsy perfume. In other words,when a perfume composition is prepared by combining the valerolactonecompound represented by the formula (II) with a woody perfume, a softand sweet milk-like odor harmonized with a woody odor can be exhibited.

Especially, when the valerolactone compound represented by the formula(II) is combined with a synthetic sandalwood-type aroma chemical, therecan be provided an odor harmonized with the woody odor of thesandalwood-type aroma chemical, which has soft and sweet milk-like woodyand balsamic odor, so that odor characteristics of natural sandalwoodcan be easily exhibited. Also, this valerolactone compound has anadvantage such as long-lasting effect In addition, the valerolactonecompound represented by the formula (I) is characterized in that thecompound has an alkyl group on position α, βor γ except position δ. Mostof valerolactones commonly used as a perfume have an alkyl substituenton position δ, and have a sweet coconut-like odor. The more the numberof the carbon atoms is, the stronger the characteristic milk-like odorbecomes, so that it is more likely to be used for food flavor due to itsodor character.

On the other hand, the valerolactone compound represented by the formula(I) has a fragrance similar to the compound having an alkyl substituenton position δ and a unique woodsy fragrance which the δ-substitutedcompound does not have; nevertheless this compound does not have analkyl substituent on position δ. Therefore, the valerolactone compoundhas an advantage that the compound is easily harmonized with variousperfumes, for instance, perfumes used in household products such asdetergents for clothes and softeners for clothes; personal care andcosmetic products such as soap, body soap, shampoo, cosmetics andperfumes; environmental hygiene products such as air fresheners,deodorants, incense sticks and candles; and the like.

In other words, since an alkyl substituent is introduced into thevalerolactone on either position α, β or γ, a compound having variouscharacteristic odor such as a woody odor, a spicy odor and a floral odortogether with a sweet odor can be synthesized. Furthermore, since anunsaturated bond is introduced into the valerolactone, the odor becomesstronger and gives various odor.

For instance, the compound represented by the formula (III) has both awoody and a spicy odor, and emits a novel and strong odor which remindsof costus and iris.

The compound represented by the formula (IV) has both a woody odor andfloral odor. In addition, this compound has a novel and soft fragranceas compared to the compound represented by the formula (III).

The compound represented by the formula (V) has a cedarwood-like woodyodor and a coumarin-like sweet odor.

The compound represented by the formula (VII) has both a woody odor anda green odor. Also, this compound has a novel odor which reminds ofsandalwood, although this fragrance is slightly weaker than that of thecompound represented by the formula (II).

Each of the valerolactone compounds represented by the formula (I) canbe included alone in the perfume composition, respectively.Alternatively, the valerolactone compounds can be used in combinationwith two or more kinds. For instance, when two or more compoundsselected from the group consisting of the compounds represented by theformula (II), the compounds represented by the formula (III), thecompounds represented by the formula (IV), the compounds represented bythe formula (V), the compounds represented by the formula (VI) and thecompounds represented by the formula (VII) are used in combination,various odor having odor characters and various strength of odor, suchas a woody odor, a floral odor, a spicy odor and a costus odor can beimparted to the compound. In addition, such combination has an advantagethat the odor can be more easily matched with the uses of the fragrancesas compared with the single use of the compound.

The compound represented by the formula (V) has a woody odor and a novelcoumarin-like sweet odor. The combination of the compound represented bythe formula (V) with the compound represented by the formula (II) isespecially suitable for the use as a substitute for a coumarin.

The valerolactone compound represented by the formula (I) can besynthesized, for instance, via a route as shown in the Scheme 1.

More specifically, an alkaline condensation reaction of an acrylonitrilederivative with a malonic acid ester derivative is carried out in thepresence of an alkali such as sodium methoxide. Subsequently, theresulting compound A can be converted to a compound B with a hydridereducing reagent such as lithium borohydride (LiBH₄). Thereafter, thenitrile moiety is hydrolyzed in the presence of an alkali (an aqueoussolution of sodium hydroxide and the like), and the resulting product istreated with an acid such as sulfuric acid, to synthesize ahydroxyvalerolactone C. The hydroxyl group of this compound is oxidizedwith an oxidizing agent such as pyridinium dichromate (PDC), to give analdehyde D. The number of carbon atoms in the aldehyde is increased byWittig reaction, and the resulting olefin is isomerized, to synthesize acompound F. In addition, the compound F′ can be easily synthesized fromthe olefin having a side chain on position γ by treating the olefin withhydrogen using a hydrogenation catalyst such as palladium/carbon (Pd/C).

Also, a compound in which R⁴ is a phenyl group can be synthesized via aroute as shown in the Scheme 2. More specifically, a compound G can besynthesized by carrying out an alkaline condensation reaction of anacrolein derivative with an aldehyde, followed by carrying out theoxidation.

The valerolactone compound represented by the formula (II) can besynthesized, as shown in the Scheme 3, by using as a starting material,propanal represented by the formula (H) or 2-methyl-2-pentenalrepresented by the formula (J). In the scheme, X represents a hydrogenatom or a metal atom. The metal atom includes alkali metal atoms such asa potassium atom and a sodium atom, alkaline earth metal atoms such as acalcium atom and a magnesium atom, and the like. When the metal atom isan alkaline earth metal atom, X in the compound represented by theformula (L) is read as X/2.

More specifically, the compound represented by the formula (K) and thecompound represented by the formula (L) are sequentially prepared bytreating propanal represented by the formula (H) or 2-methyl-2-pentenalrepresented by the formula (J) with a base. The resulting reactionsolution is treated with an acid to react the —COOX group with the —OHgroup in the compound represented by the formula (L) to form a ringclosure, and thereby the valerolactone compound represented by theformula (N) is prepared.

First, propanal or 2-methyl-2-pentenal is treated with a base. In thiscase, propanal or 2-methyl-2-pentenal can be treated with a base in asolvent.

The solvent is preferably a polar solvent from the viewpoint ofenhancing the reactivity. For instance, lower alcohols having 1 to 3carbon atoms, such as methanol, ethanol and isopropanol, and water arepreferable. Among them, the combined use of water and a lower alcohol ispreferable.

The amount of the solvent is preferably 0 to 1000 parts by weight, morepreferably 50 to 700 parts by weight, even more preferably 100 to 500parts by weight, based on 100 parts by weight of propanal or2-methyl-2-pentenal, from the viewpoint of increasing the yield andenhancing the reactivity.

The base includes alkali metal hydroxides such as potassium hydroxideand sodium hydroxide, and alkaline earth metal hydroxides such ascalcium hydroxide and magnesium hydroxide, alkali metal salts of a loweralcohol having 1 to 3 carbon atoms, such as potassium methoxide andsodium methoxide, and the like. Among them, one or more bases selectedfrom the group consisting of potassium hydroxide, sodium hydroxide,potassium methoxide and sodium methoxide are preferable.

The amount of the base is preferably 0.001 to 10 mol, more preferably0.005 to 5 mol, even more preferably 0.01 to 1 mol, per one mol ofpropanal or 2-methyl-2-pentenal.

As a method for treating propanal or 2-methyl-2-pentenal with a base,there can be cited, a method including mixing propanal or2-methyl-2-pentenal with a base, for instance, a method includingpreviously dissolving a base in a solvent and adding propanal or2-methyl-2-pentenal to the resulting solution, a method includingpreviously dissolving propanal or 2-methyl-2-pentenal in a solvent andadding a base or a solution thereof to the resulting solution, and thelike.

The atmosphere in which propanal or 2-methyl-2-pentenal is treated withthe base is not limited to specified ones. The atmosphere is preferablyan atmosphere of an inert gas such as nitrogen gas or argon gas. Thetemperature at which propanal or 2-methyl-2-pentenal is treated with thebase is not limited to specified ones. The temperature may be usually20° to 60° C.

The end point for treating propanal or 2-methyl-2-pentenal with the basecan be regarded as the time when propanal or 2-methyl-2-pentenal hasdisappeared as confirmed by, for instance, gas chromatography, thinlayer chromatography or the like. The time period required for thetreatment of propanal or 2-methyl-2-pentenal with the base cannot beabsolutely determined since the time period varies depending on thereaction conditions. The time period is usually 1 to 48 hours or so.

Next, the reaction solution obtained is treated with an acid to give avalerolactone compound.

It is preferable that water and an ether are added to the reactionsolution, the resulting solution is stirred and allowed to separate intoan aqueous layer and an ether layer, and the aqueous layer is taken outfrom the solution by removing the ether layer to use the aqueous layerin the acid treatment, prior to the treatment of the reaction solutionwith an acid.

In this case, as the ether, those commonly used such as diethyl ethercan be used. The amounts of water and the ether are not limited tospecified ones. Each amount of water and the ether is preferably 50 to200 parts by weight based on 100 parts by weight of the reactionsolution, respectively.

The acid includes inorganic acids such as hydrochloric acid andphosphoric acid; and organic acids such as acetic acid, citric acid andtartaric acid. Among them, inorganic acids are preferable.

The treatment of the reaction solution with the acid can be usuallycarried out by adding the acid to the reaction solution (aqueous layer)so that the pH of the reaction solution (aqueous layer) is 1 to 6,preferably 2 to 4, to make the solution acidic. During this treatment,the liquid temperature of the reaction solution is not limited tospecified ones, and may be usually 5° to 40° C or so. The end point ofthe acid treatment can be regarded as the time point when the pH of thereaction solution is included in the above-mentioned range, asdetermined by using a pH test paper (for instance, commerciallyavailable from Merck under the trade name of Acilit pH 0 to 6).

The valerolactone compound of the present invention is contained in thereaction mixture thus obtained by the acid treatment. The valerolactonecompound can be isolated by adding, for instance, an ether to thereaction mixture to extract a crude product, and thereafter purifyingthe crude product by the use of silica gel chromatography or the like.

The perfume composition of the present invention contains thevalerolactone compound represented by the formula (I). The valerolactonecompound represented by the formula (I) is a compound having a novelodor. Therefore, various novel odor can be easily created by combiningthis compound with various fragrances.

Examples of perfume substances which can be used in combination with thevalerolactone compound of the present invention include the followings:

hydrocarbons such as limonene, α-pinene, β-pinene, terpinene, cedrene,longifolene and valencene;

alcohols such as linalool, citronellol, geraniol, nerol, terpineol,dihydromyrcenol, ethyl linalool, famesol, nerolidol, cis-3-hexenol,cedrol, menthol, borneol, phenyl ethyl alcohol, benzyl alcohol, phenylhexanol, 2,2,6-trimethyl cyclohexyl-3-hexanol and 1-(2-t-butylcyclohexyloxy)-2-butanol;

phenols such as eugenol, thymol and vanillin;

ethers such as linalyl formate, citronellyl formate, geranyl formate,n-hexyl acetate, cis-3-hexenyl acetate, linalyl acetate, citronellylacetate, geranyl acetate, neryl acetate, terpinyl acetate, nopylacetate, bornyl acetate, isobornyl acetate, o-t-butylcyclohexyl acetate,p-t-butylcyclohexyl acetate, tricyclodecenyl acetate, benzyl acetate,styrallyl acetate, cinnamyl acetate, dimethylbenzylcarbinyl acetate,3-pentyltetrahydropyran-4-yl acetate, citronellyl propionate,tricyclodecenyl propionate, allylcyclohexyl propionate, ethyl2-cyclohexylpropionate, benzyl propionate, citronellyl butyrate,dimethylbenzylcarbinyl n-butyrate, tricyclodecenyl isobutyrate, methyl2-nonenoate, methyl benzoate, benzyl benzoate, methyl cinnamate, methylsalicylate, n-hexyl salicylate, cis-3-hexenyl salicylate, cyclohexylsalicylate, geranyl tiglate, cis-3-hexenyl tiglate, methyl jasmonate,methyl dihydrojasmonate, methyl 2,4-dihydroxy-3,6-dimethyl benzoate,ethylmethylphenyl glycidate, methyl anthranilate, and FRUITATE (tradename, commercially available from Kao Corporation);

aldehydes such as n-octanal, n-decanal, n-dodecanal, 2-methylundecanal,10-undecenal, citronellal, citral, hyroxycitronellal,dimethyltetrahydrobenz-aldehyde,4(3)-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboaldehyde,2-cyclohexylpropanal, p-t-butyl-α-methylhydrocinnamic aldehyde,p-isopropyl-α-methylhydrocinnamic aldehyde,p-ethyl-α,α-dimethylhydrocinnamic aldehyde, α-amylcinnamic aldehyde,α-hexylcinnamic aldehyde, piperonal, andα-methyl-3,4-methylenedioxyhydrocinnamic aldehyde;

ketones such as methyl heptenone, 4-methylene-3,5,6,6-tetramethyl2-heptanone, amyl cyclopentanone,3-methyl-2-(cis-2-penten-1-yl)-2-cyclopenten-1-one, methylcyclopentenolone, rose ketone, γ-methylionone, α-ionone, carvone,menthone, camphor, acetyl cedrene, isolongifolanone, nootkatone, benzylacetone, anisyl acetone, methyl β-naphthyl ketone,2,5-dimethyl-4-hydroxy-3(2H)-furanone, maltol, muscone, civetone,cyclopentadecanone and cyclohexadecene;

acetals and ketals, such as formaldehyde cyclododecylethylacetal,acetaldehyde ethylphenylpropylacetal, citral diethylacetal,phenylacetaldehyde glycerinacetal and ethylacetacetate ethylene glycolketal;

ethers such as cedryl methyl ether, anethole, β-naphthyl methyl ether,β-naphthyl ethyl ether, limonene oxide, rose oxide, 1,8-cineol anddecahydro-3a,6,6,9a-tetramethylnaphtho[2.1-b]furan; and nitriles such asgeranylnitrile and citronellylnitrile.

In addition to the carboxylic acids, there can be also used lactonessuch as γ-nonalactone, γ-undecalactone, δ-decalactone, γ-jasmolactone,coumarin, cyclopentadecanolide, cyclohexadecanolide, ambrettolide,ethylene brassylate and 1-oxahexadecanolide; natural essential oils andnatural extracts of orange, lemon, bergamot, mandarin, peppermint,spearmint, lavender, chamomile, rosemary, eucalyptus, sage, basil, rose,geranium, jasmine, ylang-ylang, anis, clove, ginger, nutmeg, cardamom,cedar, Japanese cypress, vetiver, patchouli, labdanum, and the like.

The valerolactone compound of the present invention represented by theformula (I) can be arbitrarily combined with the above-mentioned perfumesubstances. The content of the valerolactone compound in the perfume isnot limited to specified ones. The content is usually at least 0.001% byweight, preferably at least 0.01% by weight, more preferably at least0.2% by weight, still more preferably at least 0.3% by weight, even morepreferably at least 0.4% by weight, most preferably at least 0.5% byweight, from the viewpoint of providing a unique sweet and woody odor.

A perfume having a sandalwood-like odor is especially suitable for useas odor to be combined with the valerolactone compound represented bythe formula (II) since the perfume provides a perfume composition havinga high quality such as a natural sandalwood-like odor.

Examples of the perfumes having a sandalwood-like odor include thefollowing synthetic perfumes (B):

(B) one or more compounds selected from the group consisting of perfumesof which main starting material is camphorenal such as2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol,2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol,3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-pentan-2-ol,2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)- butanol,3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol and3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol;isocamphylcyclohexanols; and 3,7-dimethyl-7-methoxyoctan-2-ol; andoptical isomers of each compound mentioned above.

Among the above-mentioned synthetic perfumes (B), preferable are thefollowing components (A):

(A) one or more compounds selected from the group consisting of:2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol,3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-pentan-2-ol,2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-butanol,3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol,3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol and2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, andoptical isomers of these compounds.

The compound represented by the formula (I) and the above-mentionedperfume having a sandalwood-like odor can be arbitrarily combined. Theweight ratio of the valerolactone compound to the above-mentioned odor(B) having a sandalwood-like odor is not limited to specified ones. Theweight ratio is preferably at least 1:100000, more preferably at least1:10000, even more preferably at least 1:1000, from the viewpoint ofproviding a unique soft and sweet milk-like fragrance which is acharacteristic of natural sandalwood. Also, the above-mentioned weightratio is preferably 1:100000 to 1:1, more preferably 1:1000 to 3:7,still more preferably 1:1000 to 2:8, even more preferably 1:500 to 1:9,most preferably 1:350 to 1:9.

The perfume composition of the present invention can be prepared bymixing the above-mentioned valerolactone compound with the other perfumeby a known method. The perfume composition containing the valerolactonecompound can be used in or added to fragrant products having variousforms. The fields to which the perfume composition of the presentinvention can be applied include, for instance, household products,personal care and cosmetic products, environmental hygiene products andthe like.

The household products are ones for maintaining the functions andcleanness of homes and various products such as household commoditiesnecessary for home life. Specifically, the household products includedetergents for clothes, softeners for clothes, house cleaner, bathroomcleaner, dishwashing detergents, bleaching agents, mildew cleaners,floor waxes and the like. The perfume composition of the presentinvention can be formulated in any amounts for these goods. The amountof the perfume composition is usually 0.001 to 2% by weight, preferably0.01 to 1% by weight.

The personal care and cosmetic products are ones for keeping a personclean or beautifying a person. Specifically, the personal care andcosmetic products include soap, body shampoo, shampoo, hair careproducts, cosmetics (for instance, skin care products, make-up and thelike), perfumes, eau de colognes, antiperspirants, deodorants, bathadditives, and the like. The perfume composition of the presentinvention can be used in an arbitrary amount for these goods. Forinstance, the content of the perfume composition of the presentinvention in these goods is 0.0001 to 50% by weight. The content ispreferably 1 to 40% by weight in the case of perfumes and eau decolognes, and 0.001 to 2% by weight in the case of the goods other thanperfumes and eau de colognes, such as soap, body soap, shampoo, haircare products, cosmetic antiperspirants, deodorants and bath additives.

Also, the environmental hygiene products are ones for controlling theenvironment to a desired condition or atmosphere. Particular goodscontaining the perfume composition, capable of controlling the fragranceemitted to the environment include air freshener, deodorants, incense,incense sticks, candles and the like. The perfume composition of thepresent invention can be used in an arbitrary amount in the group ofthese products. For instance, the content of the perfume composition ofthe present invention in the goods is 0.01 to 80% by weight, preferably0.1 to 70% by weight.

Moreover, the valerolactone compound of the present invention can beused as a flavor used in foods and beverages. The valerolactone compoundcan impart characteristic sweet flavor to coffee beverages, liquors,bakery, daily products and the like, for instance, by adding thevalerolactone compound. Furthermore, the valerolactone compound of thepresent invention can be also used as a flavor for oral care products(for instance, toothpaste, mouthwash and the like) and flavors forcigarettes.

The products containing the perfume composition can be used in variousmethods, for instance, a method for applying perfume or cosmetics to adesired portion of a body to aggressively emit its fragrance; a methodfor washing clothes with a detergent to allow its fragrance to be lefton the clothes after washing; a method for spreading the fragrance inthe air by volatilizing the odor from air fresheners; a method forspreading the fragrance in the air by burning an incense stick orcandle, and the like.

In one embodiment, it is possible to impart characteristic soft andsweet odor like natural sandalwood to clothes to leave its odorremaining in the clothes by adding a perfume composition containing 1%by weight of the valerolactone compound and optionally a sandalwood-typearoma chemical to a softener for clothes in amount of 0.1% by weight ofthe softener.

EXAMPLES

Next, the present invention is more specifically explained on the basisof examples. However, the present invention is not intended to belimited to these examples.

Example 1 Synthesis of α-methyl-γ-methyl-γ-1-propenylvalerolactone

A 200 mL four-neck flask was charged with 20.13 g (0.300 mol) ofmethacrylonitrile, 52.26 g (0.300 mol) of diethyl methylmalonate and2.35 mL (0.006 mol) of a 20% sodium ethoxide solution in ethanol, andthe mixture was reacted at 90° C. for 12 hours. A buffer having a pH of6.86 was added to neutralize, and washed with saturated saline to give72.0 g of a crude product (1).

(2) Reduction, Hydrolysis and Cyclization Reactions

A 500 mL four-neck flask was charged with dehydrated tetrahydrofuran(200 mL), and stirred. The flask was charged with 6.36 g (0.290 mol) oflithium borohydride at room temperature. The reaction solution wascooled to −60° C., and the crude product (1) was added dropwise theretoover 10 minutes. The temperature of the reaction solution was graduallyraised, followed by a reaction at 0° C. for 3 hours. 10% sulfuric acid(100 mL) was slowly added dropwise to the reaction solution whilemaintaining at 0° C., to adjust the pH of the reaction solution to 4.The temperature of the reaction solution was raised to room temperature,and an aqueous sodium hydroxide solution (sodium hydroxide 37.0 g,distilled water 100 mL) was added thereto slowly.

A Dean Stark tube was attached to the flask, and the temperature of thereaction solution was raised to 85° C. to remove tetrahydrofuran fromthe reaction system, followed by a reaction at this temperature for 2.5hours. The reaction solution was transferred to a separatory funnel, andwashed with diethyl ether three times. 6N hydrochloric acid was added tothe aqueous layer to adjust the pH to 2. The aqueous layer was extractedwith ethyl acetate six times. The organic layers were combined, anddried with sodium sulfate. The solvent was removed under reducedpressure to give 38.14 g of a crude product (3). Purification by silicagel column chromatography (hexane:ethyl acetate=2: 8 (volume ratio))afforded 13.35 g of an intermediate product (3).

(3) Oxidation Reaction

A one liter four-neck flask was charged with dehydrated methylenechloride (400 mL), 13.35 g (0.084 mol) of the intermediate product (3)and 31.75 g (0.084 mol) of pyridinium dichromate, and the mixture wasreacted at room temperature for 22 hours. Diethyl ether was added to theresulting reaction solution, and the reaction solution was filtered withsilica gel to give 10.31 g of a crude product. Purification by silicagel column chromatography (hexane ethyl acetate=1:1 (volume ratio))afforded 5.60 g of an intermediated product (4).

(4) Wittig Reaction

A 300 mL four-neck flask was charged with dehydrated tetrahydrofuran (19mL) and 11.41 g (0.030 mol) of ethyltriphenyl phosphonobromide, and themixture was stirred at room temperature. To the flask was added 32.7 mL(0.030 mol) of a 0.94M phenyl lithium solution in toluene andcyclohexane, the mixture was stirred at room temperature for 30 minutes,and thereafter cooled to −30° C. A dehydrated tetrahydrofuran (12.5 mL)solution containing 4.80 g (0.03 mol) of the intermediated product (4)was added dropwise to the flask over 50 minutes, and the temperature wasraised to room temperature, followed by stirring at room temperature for10 minutes. An aqueous saturated ammonium chloride solution (10 mL) and0.1N hydrochloric acid (40 mL) were added to the reaction solution. Thereaction solution was extracted with diethyl ether three times, andwashed with an aqueous saturated sodium hydrogencarbonate solution and abuffer having a pH of 6.86 once, respectively. The solvent was removedfrom the solution under reduced pressure to give 3.20 g of a crudeproduct. Purification by silica gel column chromatography (hexane:ethylacetate=8:2 (volume ratio)) afforded 122.0 mg of an intermediate product(5).

(5) Isomerization Reaction

A 100 mL four-neck flask was charged with 588.7 mg (0.527 mmol) of theintermediate product (5), 29.0 mg (0.264 mmol) of thiophenol, 13.0 mg(0.079 mmol) of 2,2′-bisazoisobutyronitrile and benzene (15 mL), and themixture was reacted at 80° C. After the reaction for 2 hours, 13.0 mg(0.079 mmol) of 2,2′-bisazoisobutyronitrile was added again. After afurther reaction for 2 hours, 13.0 mg (0.079 mmol) ofazoisobutyronitrile was added again, and the reaction was terminatedafter 2 hours. The solvent was removed from the solution under reducedpressure, and the crude product was purified by silica gel columnchromatography (hexane:ethyl acetate)=8:2 (volume ratio)) to give 30.2mg of an end product (6).

Example 2 Synthesis of β-ethyl-γ-methyl-γ-1-propenylvalerolactone

A 100 mL four-neck flask was charged with 20.60 g (0.254 mol) of2-pentenitrile, 41.30 g (0.283 mol) of dimethyl methylmalonate and 2.60mL (0.127 mol) of 28% sodium methoxide solution in methanol, and themixture was reacted at 130° C. for 7 hours. A buffer having a pH of 6.86was added to the reaction solution to neutralize, and washed withsaturated saline to give 36.0 g of a crude product (7).

(2) Reduction, Hydrolysis and Cyclization Reactions

A 500 mL four-neck flask was charged with dehydrated tetrahydrofuran(100 mL), and stirred. The flask was charged with 3.52 g (0.162 mol) oflithium borohydride at room temperature. The reaction solution wascooled to −60° C., and the crude product (7) was added dropwise to thesolution over 10 minutes. The temperature of the reaction solution wasgradually raised, followed by a reaction at 30° C. for 3 hours. Thereaction solution was cooled to 0° C. again, and 10% sulfuric acid (65mL) was gradually added dropwise to the solution to adjust the pH of thesolution to 2. The temperature was raised to room temperature, and anaqueous sodium hydroxide solution (sodium hydroxide 20.0 g, distilledwater 80 mL) was added to the solution slowly.

A Dean Stark tube was attached to the flask, and the temperature of thereaction solution was raised to 97° C. to remove tetrahydrofuran fromthe reaction system, followed by a reaction at this temperature for 2.5hours. The reaction solution was transferred to a separatory funnel, andwashed with diethyl ether three times. To the aqueous layer was added 6Nhydrochloric acid to adjust the pH to 2, and extracted with ethylacetate six times. The organic layers were combined, and dried withsodium sulfate. The solvent was removed under reduced pressure to give25.13 g of a crude product (9). Purification by silica gel columnchromatography (hexane:ethyl acetate=3:7 (volume ratio)) afforded 12.85g of an intermediate product (9).

(3) Oxidation Reaction

A one liter four-neck flask was charged with dehydrated methylenechloride (400 mL), 12.85 g (0.075 mol) of the intermediate product (9)and 28.07 g (0.075 mol) of pyridinium dichromate, and the mixture wasreacted at room temperature for 17 hours. To the flask was added diethylether, and the reaction solution was filtered with silica gel to give11.13 g of a crude product. Purification by Kugel Rohr distillationafforded 7.17 g of an intermediate product (10).

(4) Wittig Reaction

A 100 mL four-neck flask was charged with dehydrated tetrahydrofuran (30mL) and 6.54 g (0.018 mol) of ethyltriphenyl phosphonobromide, and themixture was stirred at room temperature. To the flask was added 18.7 mL(0.018 mol) of a 0.94M phenyllithium solution in toluene andcyclohexane. The mixture was stirred at room temperature for 30 minutes,and cooled to −50° C. A dehydrated tetrahydrofruan (20 mL) solutioncontaining 3.00 g (0.018 mol) of the intermediate product (10) was addeddropwise to the solution over 20 minutes, and the temperature was raisedto room temperature, followed by stirring at room temperature for 10minutes. An aqueous saturated ammonium chloride solution (10 mL) and0.1M hydrochloric acid (40 mL) were added to the reaction solution. Thereaction solution was extracted with diethyl ether three times, andwashed with an aqueous saturated sodium hydrogencarbonate solution and abuffer having a pH of 6.86, respectively. The solvent was removed fromthe solution under reduced pressure to give 2.20 g of a crude product.Purification by silica gel column chromatography (hexane:ethylacetate=9:1 (volume ratio)) afforded 240.0 mg of an intermediatedproduct (11).

(5) Isomerization Reaction

A 100 mL four-neck flask was charged with 100.0 mg (0.550 mmol) of theintermediate product (11), 30.2 mg (0.274 mmol) of thiophenol, 13.5 mg(0.083 mmol) of 2,2′-bisazoisobutyronitrile and benzene (17 mL), and themixture was reacted at 80° C. After the reaction for 2 hours, 13.5 mg(0.083 mmol) of 2,2′-bisazoisobutyronitrile was added again. After afurther reaction for 2 hours, 13.5 mg (0.083 mmol) ofazoisobutyronitrile was added again, and the reaction was terminatedafter 2 hours. The solvent was removed from the solution under reducedpressure, and the crude product was purified by silica gel columnchromatography (hexane:ethyl acetate=8:2 (volume ratio)) to give 50.7 mgof an end product (12).

Example 3 Synthesis of α-methyl-β-ethyl-γ-methyl-γ-phenylvalerolactone

A 100 mL four-neck flask was charged with 3.92 g (0.040 mol) of2-methyl-2-pentenal, 10.74 g (0.080 mol) of 2-phenylpropanal and 20 mLof dehydrated methanol, and the mixture was stirred at 35° C. for 5minutes. 2.81 g (0.040 mol) of potassium methoxide was divided into fiveportions, and added to the mixture over 30 minutes. The temperature ofthe reaction solution was raised to 60° C., followed by stirring for18.5 hours. The reaction solution was washed with diethyl ether andhexane once, respectively, and 1N hydrochloric acid was added to thesolution to adjust the pH to 2.

After extraction with diethyl ether and hexane once, respectively, theorganic layers were combined, and washed with a buffer having a pH of6.86, and the organic solvent was removed under reduced pressure to give3.22 g of a crude product. Purification by silica gel columnchromatography (hexane:ethyl acetate=1:1 (volume ratio)) afforded 1.32 gof an end product (13).

FIG. 1 shows an ¹H-NMR (400 MHz) chart ofα-methyl-γ-methyl-γ-1-propenyl-valerolactone. FIG. 2 shows an infraredadsorption spectrum (IR) chart ofα-methyl-γ-methyl-γ-1-propenylvalerolactone. FIG. 3 shows an ¹H-NMR (400MHz) chart of β-ethyl-γ-methyl-γ-1-propenylvalerolactone. FIG. 4 showsan infrared absorption spectrum (IR) chart ofβ-ethyl-γ-methyl-γ-1-propenyl-valerolactone. FIG. 5 shows an ¹H-NMR (400MHz) chart of α-methyl-β-ethyl-γ-methyl-γ-phenylvalerolactone. FIG. 6shows an infrared absorption spectrum (IR) chart ofα-methyl-β-ethyl-γ-methyl-γ-phenyl-valerolactone.

Example 4 Synthesis ofα-methyl-β-ethyl-γ-methyl-γ-1-propenyl-δ-valerolactone from propanal

A 100 mL four-neck flask equipped with a stirrer and a thermometer wascharged with 5.10 g of distilled water, 0.48 g of a 48% aqueouspotassium hydroxide solution and 14.02 g of methanol, and the mixturewas stirred at room temperature for 5 minutes. To the resulting solutionwas added dropwise 12.57 g of propanol over 1 minute. After completionof the addition, the temperature of the resulting solution was raised to55° C., and heated to reflux for 46 hours.

Next, the resulting reaction solution was cooled to room temperature,and diluted with 100 mL of distilled water and 100 mL of diethyl etherto separate into layers. After the separation, the ether layer wasremoved, and hydrochloric acid was added to the aqueous layer to adjustthe pH to 2, followed by extraction with 100 mL of diethyl ether twotimes. The resulting organic layers were combined. The solvent wasdistilled off under reduced pressure, and purified by silica gel columnchromatography (hexane:ethyl acetate=4:1 (volume ratio)) to give 14.8 mgof α-methyl-β-ethyl-γ-methyl-γ-1-propenyl-6-valerolactone (yield 1.4%).

It was confirmed by an infrared absorption spectrum (IR) and ¹H-NMRspectrum that the resulting compound wasα-methyl-β-ethyl-γ-methyl-γ-1-propenyl-δ-valerolactone (See FIG. 7 andFIG. 8).

Example 5 Synthesis ofα-methyl-β-ethyl-γ-methyl-γ-1-propenyl-δ-valerolactone from2-methyl-2-pentenal

A 100 mL four-neck flask equipped with a stirrer and a thermometer wascharged with 7.85 g of 2-methyl-2-pentenal and 22 mL of dehydratedmethanol, and the mixture was stirred at room temperature for 5 minutes.To the reaction solution was added dropwise 1.23 g of potassiummethoxide, and the temperature of the reaction solution was raised to35° C., followed by the reaction for 6 hours. Thereafter, 20 mL ofdehydrated methanol in which 2.24 g of potassium hydroxide had beendissolved was added, and the temperature of the reaction solution wasraised to 45° C., followed by stirring for 17 hours.

Next, the resulting reaction solution was cooled to room temperature,and diluted with 100 mL of water and 100 mL of diethyl ether to separatethe solution into layers. The ether layer was removed, and the pH of theaqueous layer was adjusted to 2 with hydrochloric acid, followed byextraction with 100 mL of diethyl ether two times. The resulting organiclayers were combined, and the solvent was removed under reduced pressureand purified by silica gel column chromatography (hexane:ethylacetate=4:1 (volume ratio)) to give 1.20 g ofα-methyl-β-ethyl-γ-methyl-γ-1-propenyl-δ-valerolactone (yield 15%).

Results of measurement of infrared absorption spectrum (IR) and ¹H-NMRof the resulting α-methyl-β-ethyl-γ-methyl-γ-1-propenyl-δ-valerolactoneare shown in FIG. 7 and FIG. 8, respectively. ¹H-NMR was measured using400 MHz NMR manufactured by Varian Inc. Also, infrared absorptionspectrum (IR) was measured using Model: FT-IR manufactured by Horiba,Ltd.

In addition, mass spectroscopy of the resultingα-methyl-β-ethyl-γ-methyl-γ-1-propenyl-δ-valerolactone was measuredusing HP-5973 manufactured by Hewlett-Packard Co. The results are shownbelow.

[Results of Measurement of Mass Spectroscopy]

(m/z): 196(M+), 166(M⁺-CH₂O)

Example 6 Synthesis ofα-methyl-β-ethyl-γ-methyl-γ-propyl-δ-valerolactone

A 100 mL flask for hydrogenation was charged with 0.77 g ofα-methyl-β-ethyl-γ-methyl-γ-1-propenyl-δ-valerolactone obtained above,0.10 g of 5% Pd/C and 10 mL of ethanol, and the mixture was reacted atroom temperature for 1 hour under 0.33 MPa (hydrogen pressure: 3.36kg/cm²). Solid matters were filtered to give 0.70 g ofα-methyl-β-ethyl-γ-methyl-γ-propyl-δ-valerolactone. The results ofmeasurement of ¹H-NMR and infrared absorption spectrum (IR) of theresulting α-methyl-β-ethyl-γ-methyl-γ-propyl-δ-valerolactone are shownin FIG. 9 and FIG. 10, respectively.

Example 7 Preparation of Sandalwood Type Perfume Composition ContainingValerolactone Compound (I)

Using 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol[trade name: Sandalmysore Core manufactured by Kao Corporation] as aperfume substance having a sandalwood odor, each of perfume compositionsA₁, B₁, C₁ and D₁ was prepared in a weight ratio of perfumes A, B, C andD as shown in the following Table 1. Using a perfume E as a comparativeproduct, the fragrance of the perfume compositions was evaluated byprofessional panelists. As a result, as shown below, it was recognizedthat quality of a sandalwood odor was more enhanced by incorporation ofthe valerolactone compound represented by formula (II). TABLE 1 Perfumesubstance Having sandalwood fragrance Valerolactone (% by compound (II)weight) (% by weight) Perfume A 99.9 0.1 Perfume B 99.8 0.2 Perfume C99.5 0.5 Perfume D 99.0 1.0 Perfume E 100 0 (Comparison)<Results of Evaluation>

In the perfume composition A₁, a sandalwood note of Sandalmysore corewas enhanced as compared with the perfume E as a comparative product. Inthe perfume composition B₁, sweetness and a characteristic of naturalsandalwood were recognized as compared with the perfume E as acomparative product. In the perfume composition C₁, milk-like sweetnessand volume were enhanced as compared with the perfume E as a comparativeproduct, and effect of enhancing a characteristic of natural sandalwoodwas recognized. In the perfume composition D₁, sweetness and acharacteristic of natural sandalwood were further enhanced as comparedwith the perfume E as a comparative product.

Using 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol as aperfume substance having a sandalwood odor, the perfume composition D₂was prepared in a weight ratio of the perfume D as described in theabove Table 1, and the odor of the perfume composition D₂ was evaluatedby using the perfume E as a comparative product.

<Results of Evaluation>

In the perfume composition D₂, effect of enhancing a woody note wasrecognized as compared with the perfume E as a comparative product.

Using 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-pentan-2-ol as aperfume substance having a sandalwood odor, the perfume composition D₃was prepared in a weight ratio of the perfume D described in Table 1,and odor of the perfume composition D₃ was evaluated by using theperfume E as a comparative product.

<Results of Evaluation>

To the perfume composition D₃, a characteristic of powdery naturalsandalwood is imparted, and a soft fragrance was obtained as comparedwith the perfume E as a comparison product.

Using 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol as aperfume substance having a sandalwood odor, the perfume composition D₄was prepared in a weight ratio of the perfume D described in Table 1,and the odor of the perfume composition D₄ was evaluated by using theperfume E as a comparative product.

<Assessment Result>

In the perfume composition D₄, sweetness and volume were recognized ascompared with the perfume E as a comparative product.

The perfume substances having a sandalwood odor as shown in Table 1include, perfumes of which main starting material is camphorenal such as2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-butanol or3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol;isocamphylcyclohexanols; 3,7-dimethyl-7-methoxyoctan-2-ol, in additionto the aforementioned examples.

Example 8 Perfume Composition for Perfume

A composition for perfume showing characteristic soft and sweet woodyodor and balsamic odor having a basic natural sandalwood odor could beprepared by adding 1 part by weight of the valerolactone compoundrepresented by the formula (II) to 99 parts by weight of the perfumecomposition having the components described in the following Table 2.TABLE 2 Blended components Parts by weight SANDALMYSORE CORE*¹ 5 Methyldihydrojasmonate 4 γ-Methyl ionone 3 Bergamot oil 2 Cyclopentadecanolide1 Lemon oil 1 Benzyl acetate 0.8 Ylang-ylang oil 0.6 Citronellol 0.4Geraniol 0.4 Hexyl salicylate 0.4 Dihydromyrcenol 0.4 Ethanol 80 Total99*¹Trade name, manufactured by Kao Corporation, compound name:2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol

Comparative Example 1

When 1 part by weight of γ-ethyl-γ-butyl-δ-valerolactone was added to 99parts by weight of the perfume composition obtained in Example 8 (Table2), the resulting mixture had no sweetness, and had a strong costus-likeodor. Therefore, this mixture exhibited an unbalanced odor having nosoftness like natural sandalwood.

Comparative Example 2

When 1 part by weight of odorless dipropylene glycol was added to 99parts by weight of the perfume composition obtained in Example 8 (Table2), the resulting mixture had no sweetness, and had odor remaining of adry woodiness. Also, softness like natural sandalwood was notrecognized.

Example 9 Perfume Composition for Cloth Detergent

When 5 parts by weight of the perfume C obtained in Example 1 was addedto 95 parts by weight of the perfume composition having componentsdescribed in the following Table 3, a perfume composition for a clothdetergent showing cleanness and softness could be obtained. TABLE 3Blended components Parts by weight Orange oil 20 Methyl dihydrojasmonate15 Linalool 10 Cyclopentadecanolide 10 p-t-Butyl-α-methylhydrocinnamicaldehyde 10 α-n-Hexylcinnamic aldehyde 8 Citronellol 6 Linalyl acetate 4γ-Methyl ionone 3 Acetyl cedrene 3 o-t-Butylcyclohexyl acetate 3Dihydromyrcenol 2 Methyl β-naphthylketone 0.8 AMBROXAN*² 0.2 Total 95*²Trade name manufactured by Cognis Co. Ltd., Compound Name:Decahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan

Example 10 Detergent Composition for Cloth

The perfume composition of Example 9 in an amount of 0.4 parts by weightwas sprayed to 99.6 parts by weight of a powder detergent compositionhaving components described in the following Table 4, and 20 g of theresulting mixture was weighed. The mixture was dissolved in 30 L of hardwater having 3.5° DH. A commercially available cotton towel having aweight of 2 kg was dipped in this aqueous solution, and stirred for 5minutes, rinsed for 1 minute and dehydrated. When the flavor of thiscotton towel was evaluated, a soft and sweet odor was recognized, andthe effect of a valerolactone compound represented by the formula (II)was confirmed. TABLE 4 Blended components Parts by weight Sodium linearalkyl(C10-C18) benzenesulfonate 30 Sodium alkyl(C12-C16) sulfate 5Polyoxyethylene alkyl ether 10 Soap (C14-C20) 5 Crystallinealuminosilicate 25 Sodium carbonate 15.6 Sodium sulfate 6 Polyethyleneglycol 2 Enzyme granules 1 Total 99.6

Example 11 Perfume Composition for Cloth Softening Agent

When 8 parts by weight of the perfume D obtained in Example 7 (e.g.compositions D₁, D₂, D₃, D₄ etc.) was added to 92 parts by weight of aperfume composition having components described in the following Table5, perfume compositions for a cloth softening agent having a strong andsweet odor giving a volume to the odor could be obtained, respectively.TABLE 5 Blended components Parts by weight Muguet type fragrance 5 Rosetype fragrance 5 Jasmine type fragrance 3 Orange oil 10 Tricyclodecenylacetate 8 Tricyclodecenyl propionate 4 γ-Methyl ionone 8 Acetyl cedrene7 Benzyl salicylate 6 Phenylhexanol 5 α-n-Hexylcinnamic aldehyde 5Methyl dihydrojasmonate 4 Phenylethyl alcohol 4 Cyclopentadecanolide 4p-t-Butyl-α-methylhydrocinnamic aldehyde 3 p-t-Butyl cyclohexyl acetate3 4(3)-(4-Hydroxy-4-methylpentyl)-3-cyclohexene- 2 1-carboxyaldehydeMethyl β-naphthyl ketone 2 Anise aldehyde 2 Patchouli oil 1.5 AMBROXAN*²0.5 Total 92*²Trade name manufactured by Cognis Co. Ltd., Compound Name:Decahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan

Example 12 Softening Composition for Cloth

The perfume composition of Example 11 in an amount of 5 parts by weightwas added to 99.5 parts by weight of a softening agent compositionhaving components described in the following Table 6, and 3 g of themixture was weighed. The mixture was dissolved in 30 L of water. Acommercially available cotton towel having a weight of 2 kg was dippedin this aqueous solution, and stirred at 25° C. for 1 minute. Afterdehydration, the cotton towel was dried at room temperature; the odor ofthe cotton towel was evaluated on the next day. As a result, a naturalsandalwood-like odor was felt together with musk-like, amber-like andfloral-like odor even in a dried cloth, and sweet odor was continued.TABLE 6 Blended components Parts by weight Distearyldimethylammoniumchloride 15 (manufactured by Kao Corporation under the trade name ofQUARTAMIN D86P) Silicone compound 0.01 Calcium chloride 0.05 Ethanol 2Water 82.44 Total 99.5

Example 13 Perfume Composition for Shampoo

When 5 parts by weight of the perfume D obtained in Example 7 (e.g.compositions D₁, D₂, D₃, D₄ etc.) was added to 95 parts by weight of aperfume composition having components described in the following Table7, perfume compositions for a shampoo having a soft and sweet odorintrinsic in natural sandalwood could be obtained, respectively. TABLE 7Blended components Parts by weight Linalool 15 Cyclopentadecanolide 12Methyl dihydrojasmonate 12 p-t-Butyl-α-methylhydrocinnamic aldehyde 10Cis-3-hexenyl salicylate 10 Dimethylbenzyl carbinyl acetate 5Citronellol 5 Phenylethyl alcohol 5 AMBER CORE*³ 5 α-n-Hexylcinnamicaldehyde 4 Benzyl acetate 4 Orange oil 3 Linalyl acetate 3 γ-Methylionone 2 Total 95*³Trade name manufactured by Kao Corporation, Compound Name:1-(2-t-Butylcyclohexyloxy)-2-butanol

Example 14 Perfume Composition for Liquid Body Shampoo

When 10 parts by weight of the perfume D obtained in Example 7 (e.g.compositions D₁, D₂, D₃, D₄ etc.) was added to 90 parts by weight of aperfume composition having components described in the following Table8, perfume compositions for a liquid body shampoo characterized inremaining of a soft and sweet odor on a skin could be obtained,respectively. TABLE 8 Blended components Parts by weight Muguet typefragrance 15 Rose type fragrance 10 Linalool 8 AMBER CORE*³ 8 Methyldihydrojasmonate 8 Orange oil 5 β-Ionone 5 n-Hexyl salicylate 5o-t-Butyl cyclohexyl acetate 5 Cyclopentadecanolide 5 Patchouli oil 44(3)-(4-Hydroxy-4-methylpentyl)-3-cyclohexene- 4 1-carboxyaldehydeDimethylbenzyl carbinyl n-butyrate 4 γ-Undecalactone 2 Piperonal 2 Total90*³Trade name manufactured by Kao Corporation, Compound Name:1-(2-t-Butylcyclohexyloxy)-2-butanol

Example 15 Perfume Composition for Incense Stick

When 5 parts by weight of the valerolactone compound represented by theformula (II) was added to 95 parts by weight of a perfume compositionhaving components described in the following Table 9, a perfumecomposition for an incense stick having an oriental sweet odor likeperfume could be obtained. TABLE 9 Blended components Parts by weightBergamot oil 10 Patchouli oil 10 Vetiver oil 3 Cinnamon oil 1 Nutmeg oil1 Clove bud oil 1 Dihydromyrcenol 10 Linalool 3 SANDALMYSORE CORE*1 10Isocamphyl cyclohexanol 10 AMBER CORE*³ 10 Acetyl cedrene 10Cyclopentadecanolide 10 Vanillin 4 Piperonal 1 Cistus landaniferabsolute 1 Total 95*1Trade name manufactured by Kao Corporation, Compound name:2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol*³Trade name manufactured by Kao Corporation, Compound name:1-(2-t-butylcyclohexyloxy)-2-butanol

Example 16 Flavor Composition for Imparting Milk Flavor

When 0.8 part by weight of the valerolactone compound represented by theformula (II) was added to 99.2 parts by weight of a flavor compositionhaving components described in the following Table 10, a perfumecomposition for imparting a milk flavor, having volume and a naturalmilk flavor could be obtained. TABLE 10 Blended components Parts byweight Dimethyl sulfide 0.01 Cis-3-hexenol 0.05 2-Nonanone 0.022-Undecanone 0.03 Acetoin 0.01 Diacetyl 0.01 Butyl dibutyryl lactate0.10 Ethyl levulinate 0.05 Ethyl myristate 0.20 Ethylhexanoate 0.20δ-Undecalactone 1.00 δ-Dodecalactone 1.20 Butyric acid 0.30 Octanoicacid 0.30 Decanoic acid 1.00 Lauric acid 1.00 Myristic acid 0.10 Ethylmaltol 0.10 Vanillin 0.10 Propylene glycol 93.42 Total 99.20

Example 17 Milk Coffee Composition

When 0.1 part by weight of the flavor composition of Example 16 wasadded to 99.9 parts by weight of a milk coffee composition havingcomponents described in the following Table 11, a milk coffeecomposition having rich sweetness and a suitable bitter flavor could beobtained. TABLE 11 Blended components Parts by weight Regular coffee6.00 Coffee extract 2.00 Skim milk powder 0.60 Whole milk powder 0.70Granulated sugar 8.00 Sugar ester 0.06 Sodium hydrogen carbonate 0.08Coffee flavor 0.10 Water 82.36 Total 99.90

Example 18 Perfume Composition

When 50 parts by weight of the valerolactone compound (II), 10 parts byweight of the valerolactone compound (III), 30 parts by weight of thevalerolactone compound (IV) and 10 parts by weight of the valerolactonecompound (VII) were mixed together, a woody and sandal-like perfumecomposition reminding of floral and costus was obtained.

Example 19 Perfume Composition

When 40 parts by weight of the valerolactone compound (II) was combinedwith 60 parts by weight of the valerolactone compound (V), a coumarintype perfume composition reminding of a woody odor and a coumarin-likesweetness odor was obtained.

INDUSTRIAL APPLICABILITY

The valerolactone compound can be arbitrarily combined with variousperfumes. The perfume composition containing the valerolactone compoundcan be used in or applied to various aromatic products, for example, inthe field of household products, personal and cosmetic products, andenvironmental hygiene products.

1. A valerolactone compound represented by the formula (I):

wherein each of R¹ and R² is independently a hydrogen atom, a methylgroup or an ethyl group, wherein when R¹ is a hydrogen atom, R² is not ahydrogen atom; and wherein when R² is a hydrogen atom, R¹ is not ahydrogen atom, R³ is a hydrogen atom or a methyl group, and R⁴ is apropyl group, a 1-propenyl group or a phenyl group.
 2. A valerolactonecompound represented by the formula (II):


3. The valerolactone compound according to claim 2, obtained by acting abase on propanal, and treating the resulting reaction solution with anacid.
 4. The valerolactone compound according to claim 3, wherein saidbase is one or more compounds selected from the group consisting ofpotassium hydroxide, sodium hydroxide, potassium methoxide and sodiummethoxide.
 5. A process for preparing a valerolactone represented by theformula (II):

comprising acting a base on propanal, and treating the resultingreaction solution with an acid.
 6. A process for preparing avalerolactone represented by the formula (II):

comprising acting a base on 2-methyl-2-pentenal, and treating theresulting reaction solution with an acid.
 7. The process for preparing avalerolactone compound according to claim 5 or 6, wherein said base isone or more compounds selected from the group consisting of potassiumhydroxide, sodium hydroxide, potassium methoxide and sodium methoxide.8. A perfume composition comprising a valerolactone compound representedby the formula (I):

wherein each of R¹ and R² is independently a hydrogen atom, a methylgroup or an ethyl group wherein when R¹ is a hydrogen atom, R² is not ahydrogen atom; and wherein when R² is a hydrogen atom, R¹ is not ahydrogen atom., R³ is a hydrogen atom or a methyl group, and R⁴ is apropyl group, a 1-propenyl group or a phenyl group.
 9. A perfumecomposition comprising a valerolactone compound represented by theformula (II):


10. A perfume composition comprising the valerolactone compound asdefined in claim
 3. 11. The perfume composition according to claim 8 or9, further comprising one or more compounds selected from the groupconsisting of the following compounds represented by the formulae (III)to (VII):


12. The perfume composition according to claim 8 or 9, wherein thecontent of said valerolactone compound is at least 0.001% by weight. 13.The perfume composition according to claim 9, wherein the content ofsaid valerolactone compound is at least 0.2% by weight.
 14. A perfumecomposition comprising two or more compounds selected from the groupconsisting of the following compounds represented by the formulae (III)to (VII):


15. The perfume composition according to any one of claims 8 to 10,further comprising a perfume of which main starting material is acamphorenal.
 16. The perfume composition according to any one of claims8 to 10, further comprising one or more compounds selected from thegroup consisting of the following components (A): (A)2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol,3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-pentan-2-ol,2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-butanol,3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol,3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol,2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, andoptical isomers thereof.
 17. The perfume composition according to claim16, wherein the weight ratio of the compound represented by the formula(I) to the component (A) is at least 1:100,000.
 18. The perfumecomposition according to claim 16, wherein the weight ratio of thecompound represented by the formula (I) to the component (A) is at least1:500.
 19. A household product comprising the perfume composition asdefined in any one of claims 8 to
 18. 20. A personal care and cosmeticproduct comprising the perfume composition as defined in any one ofclaims 8 to
 18. 21. An environmental hygiene product comprising theperfume composition as defined in any one of claims 8 to
 18. 22. Abeverage comprising the perfume composition as defined in any one ofclaims 8 to
 18. 23. A food comprising the perfume composition as definedin any one of claims 8 to 18.